Wave set compositions containing a polysaccharide



United States Patent US. Cl. 132-7 13 Claims ABSTRACT OF THE DISCLOSUREThis invention relates to hair control compositions comprising apolysaccharide consisting essentially of a polymeric chain ofglucopyranose units. The compositions are adapted to form a film abouthair filaments without flakiness.

This application is a continuation-in-part of a prior applicationbearing the title Polysaccharides and Methods for Production Thereofhaving Ser. No. 449,581, filed Apr. 20, 1965, and now abandoned.

This invention relates to improved hair control compositions and tomethods for their employment in hair application. More particularly, theinvention relates to novel polysaccharide hair control compositionsadapted to impart to the hair improved maintenance of the desiredconfiguration.

Heretofore various natural gums such as gum karaya, acacia, tragacanth,and quince seed etc. have been employed in hair control compositions toprovide a coating about hair filaments. However, due to the lack ofstandardization, the natural gums and their application in wave setcompositions has been severely limited. Viscosities and other propertiesof natural gums will vary greatly from batch to batch depending on thesource of material, climate, soil, method of extraction and otherreasons which are difiicult if not impossible to control.

Various synthetic polymers have been offered for this purpose; however,such gums have a tendency to cause flakiness when the drying vehicle isevaporated. Moreover, many of the synthetic polymers have a disagreeableodor which often is impossible to mask. Among the synthetic polymers,polyvinylpyrrolidone has found extensive use in hair controlcompositions. However, when it is used in substantial quantitiesnecessary to provide an adequate film an objectionable, sticky film aswell as flakiness occurs. Another disadvantage of polyvinylpyrrolidoneis that when it is applied or exposed to conditions wherein a relativehumidity is greater than 50- percent, the resultant film becomes tackyand the hair thus loses its set.

It is an object of the present invention to provide a novelpolysaccharide hair control composition capable of providing superiorfilms on hair filaments.

A further object is to provide a polysaccharide hair control compositionadapted to form a film about the hair filaments without concomitantfiakiness.

According to the present invention, there is provided a novel haircontrol composition adapted to form a film about an air filament whichcomprises water and a polysaccharide consisting essentially of apolymeric chain of glucopyranose units, the glucopyranose units beingcontiguously attached to another by a beta 1,3 linkage to form apolymeric chain, said polymeric chain having side chain glucopyranoseunits contiguously attached to the polymeric chain through a beta 1,6linkage.

ice

The polysaccharide employed hereein may be further represented by thestructural formula:

GI! G G a. G G G a.

n 'b 0- 'd- B- 'i z 5 L I wherein G is a glucopyranose unit of theformula:

i c H2. 0.-

H H o H H OH H at! which is contiguously attached to the adjacentglucopyranose units through a beta 1,3 linkage in the polymeric chainand also appended to another glucopyranose unit through a beta 1,6linkage to form a side chain. G is glucopyranose units of the formula:

H CH;

G" is a glucopyranose unit attached to the G glucopyranose unit througha beta 1,6 linkage of the formula:

CHzOH H L OH H H OH N is an integer, and a, b, c, d, e, f, and g areintegers from 0 to 1 such that the ratio of the sum of G units to Gunits (ie.,

gentiobiose) ranges from 3:1 to 4:3. Advantageously, a,

b, c, d, e, f, and g are values that the ratio of the sum of G units toG units (gentiobiose) ranges from about 5:2 to about 3:2 with a ratio ofbetween 2:1 to 3:2 providing superior properties when thepolysaccharides are employed in an aqueous system.

The fermentate polysaccharides are further characterized by thefollowing:

(a) Yielding only D-glucose when subjected to hydrolysis by 1 N sulfuricacid at approximately 100 C.;

(b) Yielding from about 20 to about 30 mole percent formic acid and afirst residue when subjected to periodate oxidation as ascertained bythe conventional analytical technique of carbohydrate chemistry which ismore fully described by F. Smith and R. Montgomery, The Chemistry ofPlant Gums and Mucilages, Reinhold (New York, 1959), pp. 144-222;

(c) Said first residue yielding from about 20 to about 30 mole percentglycerol and an insoluble second residue when subjected to reduction bysodium borohydride followed by hydrolysis with dilute sulfuric acid'(eg. 0.1 N at 20 C. for six hours);

((1) Said second residue yielding only D-glucose when subjected to theenzymaticaction of the beta 1,3 D- glucanase which is derived from theorganism Basidimycete No. 806 and (e) Yielding a Weight ratio ofD-glucosee to gentiobiose ranging from about 3:1 to about 4:3 andadvantageously ranging from about 5:2 to about 3:2 and most preferablybetween 2:1 and 3:2 when the polysaccharide is subjected to theenzymatic action of the beta 1,3 D- glucanase which is derived from theorganism Basidiomycete No. 806 (Le. the ratio of G G: I

The polysaccharides have a terminal aldehyde and glucose units. Typicalmolecular weights of the polysaccharide are those that have an averagemolecular weight in excess of 19,000. Preferably employed are those polysaccharides having an average molecular weight of at least 50,000 withpolysaccharides having an average molecular weight in excess of 100,000being most preferred. Exemplary polysaccharides are those having amolecular weight ranging from about 20,000 to about 300,000.

The polymers employed in the instant hair control compositions areprepared by the reaction of certain organisms hereinafter disclosed in amedium containing a carbohydrate source material. Organisms whichproduce members of the polysaccharides herein disclosed include:Sclerotium glacanicum, Pillsbury Culture Code No. 13, n.s.p. (NRRL3006); Sclerotium delphinlii Jersveld/ Welc'h, American Type CultureCollection No. 15198, (Source: Centraalbureau Voor SchimmelculturesBaarn, Netherlands); Sclerotium delphinii Welch/White, American TypeCulture No. 15200; Sclerotiwm rolfsii Barnett, American Type CultureCollection No. 15203; Sclerotz'w'm rolfsii Barnett, American TypeCulture Collection No. 15206; Sclerotium rolfsii Barnett, American TypeCulture Collection No. 15201; Sclerotium rolfsii Barnett, American TypeCulture Collection No. 15205; Sclerotium rolfsii Gilrnan, American TypeCulture Collection No. 15195; Sclerotium delphinii Gilman, American TypeCulture Collection No. 15197; Sclerotium delphinii Stevens I, AmericanType Culture Collection No. 15194; Sci-erotium delphinii Welch/ Mix,American Type Culture Collection No. 15199; Sclerotium' delphiniiSteven, American Type Culture Collection No. 15196. Sclerotiumcoffeicolwms Stahel, American Type Culture Collection No. 15208;Sclerotium rolfsii QM, American Type Culture Collection No. 15202;Sclerotium rolfsii QM, American Type Culture Collection No. 15204;Corticium rolfxii Curzi/Balducci, American Type Culture Collection No.15211; Corticium rolfsii (Sacc) Curzi, American Type Culture CollectionNo. 15212; Corticium' rolfsii Curzi/Ficus, American Type CultureCollection No. 15209; Sclerotinia gladoli American Type CultureCollection No. 15207; Stromalim'a narcissi Groves, American Type CultureCollection No. 15213.

Suitable carbohydrate source materials for preparing the polysaccharidevia the above-mentioned organisms include sucrose, D-xylose, D-mannose,D-glucose (dextrose), L-arabinase, D-g-alactose, D-fructose, maltose,melezitose, raflinose, methylbeta-maltoside, aesculin, celiobiose,trehalose, L-rhamnose, cellulose and xylan or mixtures thereof.

In preparing the polysaccharides herein employed the carbohydrate sourcematerial is dissolved in an aqueous solution generally at aconcentration ranging from about 3 to percent by weight along with otherculture medium nutrients such as a yeast extract and mineral salts (e.g.Czapek Dox Broth).

The organism is then added to the culture medium, the pH is adjustedbetween about 3-6 and the temperature is maintained between about 2535F. (e.g. for about 3-6 days) whereby the polysaccharide is formed. Thepolysaccharide is then isolated from the medium and washed with analcohol (e.g. methanol).

The hair control compositions of the instant invention Au organism in acollection maintained by the Microbiology Lab, Quartermaster Research 0;Engineering Center, Nattck, Mass.

provide many advantages over those heretofore known. Included among suchadvantages is that when the hair control composition is applied to thehair, it produces a lustrous but natural looking film or sheath abouteach hair filament. Exposed to humid conditions the film about the hairfilaments retains its identity and has an ability to absorb and retainmoisture without concomitant development of tackiness or flakiness. Thepolysaccharide sheath is sufliciently sensitive to be removed from thehair by water washing (e.g. with a mild shampoo). Due to thepolysaccharide film forming characteristic it is now possible to employa lesser amount of polymer than heretofore used. An additional benefitprovided over that of synthetic polymers conventionally employed issuperior lubricity. This lubricity is similar to that derived fromnatural materials; however the instant polysaccharide provides a gurustandardization which was heretofore lacking from the natural gums. Thehair conditioning composition provides excellent reset characteristicswhen hair previously treated and dried is subsequently combed with a wetcomb.

Normally, the composition of this invention will contain from about 0.1percent by weight to about 2.5 percent by weight of the polysaccharidebased upon the total weight amount of Water in the hair controlcomposition. Advantageously, the amount of the polysaccharide in thehair control composition ranges from about .25 to about 1.5 weightpercent with an amount ranging from about .3 weight percent to about 1.0weight percent being preferred. Also contemplated with the presentinvention are concentrated hair control composition which may besubsequently diluted by the ultimate consumer.

Various hair control ingredients conventionally added to hair controlcompositions such as the natural and synthetic polymer, preservatives,coloring agents, perfumes and auxiliary drying agents, etc. andadaptable to the hair control compositions of the instant invention.

Typical natural polymers and derivatives thereof, although notnecessarily included in the hair control composition herein provided,include gum karaya, acacia, tragacanth, quince seed, shellac, sodiumalginate, bleached dewaxed shellac etc. Exemplary synthetically producedpolymers include polyvinylpyrrolidone, maleic anhydrideethylene oxidecopolymers, copolymer of N-vinyl-e-caprolactam, copolymers of vinylpyrrolidone and vinyl ester of fatty acids such as vinyl acetate, vinylstearate, methyl acrylate, copolymers of laurylmethacrylate anddiethylaminoethyl methacrylate which has 'been reacted with an alkylhalide or sulfate such as methyl chloride or dimethyl sulfate to form aquaternary ammonium salt thereof, water soluble polyacrylic resins, etc.

To prevent microbial action a preservative is generally added to thewave control composition in an amount sufficient to prevent microbialdegradation. Suitable pre servatives are those conventionally used inthe art to prevent microbial action and especially those previouslyemployed in the hair control composition art. Typical preservatives arethe alcohols (e.g. ethyl, butyl and propyl); organic acids such asbenzoic acid, salicylic acid, sorbic acid and salts thereof (eg thesodium and calcium salts); p-chloro-m-xylenol; dichloro-m-xylenol;methyl chloro-thymol; 2,2'-methylenebis-(3,4,6-trichlorophenol),3acetyl-6-methyl-2H-pyran-2,4 (3H)-di0ne and sodium salt thereof; theesters of p-hydroxybenzoic acid such as methyl, ethyl, propyl and butyl,etc.

The aqueous polysaccharide solutions are odorless and will not maskvarious perfumes conventionally added to hair control compositions. Incombination with perfumes the resulting composition produces an enhancedolefactory sense when compared to that of prior art hair controlcompositions containing perfumes. Perfumes adaptable herein includeconventional perfumes such as one or more of the naturally occurringessential oils, one or more specific odorous synthetic organiccompounds, or a blend of these essential oils and organic compounds.Citronella oil,

lemon oil, and bois de rose oil are representative of essential oilperfumes. Conventionally employed odorous organic material includecitronella, vetiverol acetate, methyl phenyl carbinyl acetate, phenylethyl acetate, hydroxycitronella and phenyl ethyl alcohol.

The hair control compositions may be applied to the hair by any suitablefashion such as by an atomizer, hand application or by an aerosolsystem. A typical aerosol system consists of a pressure package having avalve-controlled outlet containing a gaseous or volatile liquidpropellant and the wave control composition of the present invention,illustrative of the usual gaseous or liquified gas propellants arenitrogen; carbon dioxide; nitrousoxide; the lower alkanes (e.g. propane,isobutane, etc.) and preferably the saturated, halogenated aliphatic,hydrocarbons known by the trade name Freon and which include, forexample, 1,1-difluoroethane; 1,2-dichloro-l,1,2,2-tetrafiuoroethane;trichlorotrifiuoroethane; dichlorodifluoro methane; monochlorodifluoromethane; monochlorotrifluoro methan; 1-monochloro-1,l-difluoroethane, ormixtures thereof. The amounts of volatile liquid propellants employedmay vary over a wide range depending upon whether and to what extent thefilm forming material is soluble therein, larger quantities beingemployed when it dissolves the polysaccharide. Generally, the entireamount of volatile liquid propellant will be from 100 percent to 300percent, preferably not over 230 percent by weight of the hair controlcompositions. In an aerosol system the amount of polysaccharide basedupon the total water content generally ranges from about 0.1 to about 1weight percent with an amount ranging from about 0.2 to about .75 beingpreferred.

The following examples are illustrative of the inven tion:

EXAMPLE I (A) Preparation of the polysaccharide Into a sterile culturemedium consisting of:

300 parts distilled water 9 parts sucrose 0.9 part NaNO 0.3 part K HPO0.15 part KCl 0.3 part autolyzed yeast 0.003 part FeSO was inoculatedwith a loopful of Sclerotium rolfsii Barnett, American Type CultureCollection No. 15206 and incubated for 3 days at approximately 28 C. ona rotary shaker. The resultant culture was placed in a sterile blender,homogenized and set aside for use as an inoculum.

An aqueous carbohydrate source was prepared by dissolving the followingingredients in 500 gallons of water.

Ingredients: Pounds Glucose 86 Magnesium sulfate 6.45 Potassiumdihydroorthophosphate 4.3 Sodium nitrate 8.6 BBL yeast extract 4.3

The pH of the resulting medium was adjusted to 4.5 with hydrochloricacid and then heated for one hour at 15 psi. and pressure at 250 F.

After the cultured medium had cooled, 15 pounds of the previouslyprepared homogenized inoculum was added to a fermenter vessel equippedwith variable speed agitation, a sterile air supply and temperaturecontrol means. The medium was incubated for 5 days at a temperature of28 F. and at an agitation rate of 96 rpm. and an aeration rate of 0.1vol./ vol. of medium per minute. The fermentate was then removed into asmaller vessel to which 129,000 pounds of water were added. Afterthorough mixing the diluted fermentate was heated to approximately 90 to95 C., cooled, and then filtered via a diatamaceous earth filter forremoval of mold cells.

To the filtrate an equal volume of methanol was added. Within a fewminutes, the product rose to the surface as a fibrous mass and wasremoved therefrom by skimming. The polysaccharide was washed twice witha methanol and then dried in an oven at 50 C. The resultant fibrous matof polysaccharide was then comminuted to a fine powder.

Polysaccharide chemical and physical results Viscosity of aqueoussolutions.-After 24 hours (Brookfield viscometer23 C.30 r.p.m.-No. 3spindle):

Cps. 1.0% 2200 1.25% 3280 1.5% About 4400 Additional informationrelating to the preparation of other polysaccharides and polysaccharidesthereof is disclosed in my copending application S.N. 449,581.

Preparation and use of the hair conditioning composition A 0.35 aqueoussolution of the polysaccharide prepared in accordance with Example I wasapplied to extremely fine and dry hair by hand application until thehair was thoroughly wetted. The hair was then curled into the desiredhair style and allowed to dry. The hair thus treated had a more lustrousbut natural appearance. The hair set was soft and silky in appearancewith more than sufficient rigidity to maintain the set. Each hairfilament was provided with a separate coating or sheath ofpolysaccharide film without concomitant matting between the hairfilaments. Changes in relative humidity failed to effect the set with nodevelopment of flakiness or tackiness resulting therefrom. By employinga wetted comb it was possible to change the hair style by resetting thehair.

The hair set was readily removed from the hair by washing with water.

What is claimed is:

1. A hair control composition adapted to provide a shaped mass of hairby coating the hair filaments with a polysaccharide, said compositioncomprising an aqueous solution of a olysaccharide consisting essentiallyof a polymeric chain of glucopyranose units, said glucopyranose unitsbeing contiguously attached to one another by a beta 1,3 linkage to forma polymeric chain, said polymeric chain having beta 1,6 glucopyranoseunits contiguously attached to the polymeric chain through a beta 1,6linkage.

2. The hair control composition according to claim 1 wherein the amountof polysaccharide based upon the amount of water ranges from about .2percent by weight to about 2 percent by weight and the polysaccharide isfurther characterized by yielding a weight ratio of D-glucose togentiobiose from about 2:1 to about 3:2 when the polysaccharide issubjected to the enzymatic action of a beta 1,3 D-glucanase which isderived from the organism Basidiomycete QM No. 806.

3. The hair control composition according to claim 2 wherein the amountof polysaccharide ranges from about .5 to about 1.0 weight percent basedupon the total amount of the molecular weight of the olysaccharide is atleast 50,000.

4. The hair control composition according to claim 3 wherein thepolysaccharide is characterized by yielding a weight ratio of D-glucoseto gentiobiose of about 2:1 when the polysaccharide is subjected to theenzymatic 7 action of a beta 1.3 D-glucanase which is derived from theorganism Basidiomycete QM No. 806.

5. The hair control composition according to claim 4 wherein thepolysaccharide is characterized by yielding a weight ratio of D-glucoseto gentiobiose of about 3:2 when the polysaccharide is subjected to theenzymatic action of a beta 1,3 D-glucanase which is derived from theorganism Basidiomycete QM No. 806.

6. A package comprising a pressure-tight container having avalve-controlled outlet and containing (a) an improved hair controlcomposition comprising an aqueous solution of a polysaccharide whereinthe polysaccharide consists essentially of a polymeric chain ofglucopyranose units, said glucopyranose units being contiguouslyattached to one another by a beta 1,3 linkage to form a polymeric chain,said chain having beta 1,6 glucopyranose units contiguously attached tothe polymeric chain through a beta 1,6 linkage and (b) a propellant inan amount sufiicient to force said hair control composition out of thecontainer.

7. The package according to claim 6 wherein the polysaccharide has amolecular weight in excess of 19,000 and is rfurther characterized byyielding a weight ratio of D-glucose to gentiobiose from about 2:1 toabout 3:2 when the polysaccharide is subjected to enzymatic action of abeta 1,3 D-glucanase which is derived from the organism Basidiomycete QMNo. 806.

8. The package according to claim 7 containing a polysaccharide which ischaracterized by a weight ratio of D- glncose to gentiobiose of about2:1 when subjected to the enzymatic action.

9. The packaging according to claim 8 containing a polysaccharide whichis characterized by a weight ratio of D-glucose to gentiobiose of about3:2 when subjected to the enzymatic action.

10. A process of shaping human hair and hair filaments comprising thesteps:

(a) applying to the hair an aqueous solution of a polysaccharide, thepolysaccharide consisting essentially of a polymeric chain ofglucopyranose units, said glucopyranose units being contiguouslyattached to one another through a beta 1,3 linkage to form a polymericchain, said polymeric chain having beta 1,6 glucopyranose unitscontiguously attached to the polymeric chain through a beta 1,6 linkage,said solution forming a pliable mass of hair filaments,

(b) working and shaping the pliable mass into a desired form, and

(c) drying the shaped mass thus forming a coating about the hairfilaments capable of retaining the hair in the desired form.

11. The process according to claim 10 wherein the polysaccharide has anaverage molecular weight in excess of 19,000, said polysaccharide beingfurther characterized by yielding a weight ratio of D-glucose togentiobiose from 2:1 to about 3:2 when the polysaccharide is subjectedto enzymatic action of a beta 1,3 D-glucanase which is derived from theorganism Basidiomycete QM No. 806.

12. The process according to claim 11 wherein the polysaccharide has anaverage molecular Weight of at least 50,000 and the weight ratio ofD-glucose to gentiobiose is about 2:1 when said polysaccharide issubjected to enzymatic action of a beta 1,3 D-glucanase which is derivedfrom the organism Basidiomycete QM No. 806.

13. The process according to claim 11 wherein the polysaccharide has anaverage molecular weight of at least 50,000 and the weight ratio ofD-glucose to gentiobiose is about 3:2 when said polysaccharide issubjected to enzymatic action of a beta 1,3 D-glucanase which is derivedfrom the organism Basidiomycete QM No. 806.

References Cited UNITED STATES PATENTS 2,056,135 9/1936 -But1er 42471ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US.Cl. X.R.

